Taming, Training and Combining Subvalent Main-Group Cations of Group 13 and 14

在这个扩展项目中，最终目标是弥合从收集更重的13基团阳离子的美丽“蝴蝶”阶段的差距，即具有不寻常结构和键合性质的化合物，到一个系统，在添加定义和商业上可用的螯合膦配体后，产生功能分子，合作作为trans-bent二聚体或单独作为类似碳的单体，可以激活键。正电荷稳定了单价阶段，有利于还原消除。因此，该提案描述了两种典型的催化循环，以产生与项目相关的过程，如硼氢化：一方面是基于氧化加成和还原消除的机制，另一方面是基于氧化加成后形成的刘易斯酸三价氧化产物的刘易斯酸机制。此外，本项目将对刚刚打开的Al(I)阳离子的化学性质进行扩展，将打开14族阳离子（Si-Pb）的芳香配合物，并将研究13族和14族阳离子结合成杂双金属簇阳离子。特别是，基团14的芳香配合物实际上是没有先例的，成功的获得将需要丰富的后续化学反应，例如，通过与更多富电子的供体反应和利用连接的指示物的非成键ns2轨道的轨道能量。因此，在项目的第二部分，“蝴蝶”再次在新的领域被专门寻找，然后被驯服并发挥作用。因此，这个项目的标题表明了我们的目标：“驯服、训练和结合第13和14组的亚价主群职务”。

In this extension project, the final goal is to bridge the gap from the stage of collecting beautiful "butterflies" of the heavier Group 13 cations, i.e., compounds with unusual structural and bonding properties, to a system that, upon addition of defined and commercially available chelating phosphane ligands, generates functional molecules that, cooperatively as trans-bent dimers or alone as carbene-analogous monomers, can activate bonds. The positive charge stabilizes the univalent stage and facilitates reductive elimination. Hence, the proposal describes two typical catalytic cycles for resulting project-relevant processes like hydroboration: On the one hand, a mechanism basing on oxidative addition and reductive elimination, and an alternative, Lewis acidic mechanism based on the Lewis-acidic trivalent oxidation products formed after oxidative addition. Further, the chemistry of the Al(I) cations just opened will be extended in the project, access to aromatic complexes of group 14 dications (Si-Pb) will be opened, and the combination of group 13 and 14 cations into heterobimetallic cluster cations will be investigated. In particular, the group 14 dication aromatic complexes are virtually without precedent and successful access would entail rich follow-up chemistry, e.g., by reaction with more electron-rich donors and playing with the orbital energy of the nonbonding ns2 orbitals of the ligated dications. In the second part of the project, therefore, "butterflies" are again specifically sought for in new territory, which are then to be tamed and brought to function. Hence, the title of the project indicates our goals: „Taming, Training and Combining Subvalent Main-Group Cations of Group 13 and 14“